Process of effecting catalytic reactions.



UNITED STATES PATEN oTTo CHRISTIAN HAGEMANN, or YONKERS, AND CHARLESBASKERVILLE, or NEW ronx, n. Y.

PROCESS OF EFFECTING CATALYTIC REACTIONS.

1,238,137. No Drawing.

To all whom it may concern:

Be it known that we, OTTo CHRISTIAN HAGEMANN, a subject of the King ofGreat Britain, residing at Yonkers, N.'Y., and Dr. CHARLES BASKERVILL'E,a citizen of the United States, residing at New York, N. Y., haveinvented new and useful Improvements in Processes of Effecting CatalyticReactions, of which the following is a spear fication.

The present invention relates to catalytlc processes, and has specialapplication in the art of hydrogenating oils, such as cotton seed or thelike, also oxidation of oils, such as linseed or other drying oils,either with oxygen or ozone, and also is applicable 1n the effecting ofvarious gas reactions, and other reactions depending upon the presenceof a catalytic body.

In our copending application, Serial No. 747,181, (Patent No. 1,083,930,Jan. 13,1914) we have described and claimed, the use of nickel orsimilarly acting catalytic metal as a catalyst in various reactions,especially the' reaction of hydrogen gas upon liquid oils, for theroduction of hardened oils or fats, said nic el being in a particularmechanical condition.

In the present invention the catalyst which we preferably employ isnickel, or an alloy of nickel with a small amount of cobalt, having allona part of its surface oxidized. Since the tfuse of this metal, in theform of extremely thin leaf of a thickness of one twenty-thousandth toone fortythousandth of an inch, of which the surface portions areoxidized is already covered in our patent above referred to, the presentcase is restricted to metal forms, having an oxidized surface, (all orpart only) said metal being in more massive forms, that is to say thecatalytic body is in the form of pieces, of which the smallest dimensionis materially greater than one twenty-thousandth of an inch. In otherwords the present case relates to the use of the metal in forms otherthan leaves, and with portions of the surface oxidized, as more fullydescribed farther on.

We have discovered that more uniform reliability of catalytic action bysuch metallic nickel shapes can be secured when previously applying tosuch nickel shapes, such Specification of Tetters Patent.

Patented A11 28, 1917.

Application filed January 12, 1914. Serial No. 811,734.

as wire or sheets, etc., a very slight surface oxidation.

As in our prior application above referred to, the revivification orregeneration of the catalyzer after use, can be effected by furtheroxidizing, and then reducing the oxidized surface of said nickel shapesor bodies, after which inthe present process a slight surface oxidationis again effected prior to the further use of the catalytic body ormaterial. Or we may, in revivifying the catalyzer after use, dispensewith the step of reduction, and re-use the metal shapes aforesaid afterhaving previously applied to them slight surface oxidation.

In carrying out the process, we may employ a stationary catalyzer, andmove the oil to be treated and the gasfor effecting the desiredreaction, in opposite directions over said catalyzer, or the oil may beplaced in a receptacle, the gas introduced near the 1 bottom of thereceptacle, and the mass of oil and catalyzer agitated, in order tobring about complete reaction between various portions of the oil andthe reactive material. In this mode of treatment the catalyzer may bemade in the form of a stirring or agitating member, for example of wiregauze, or thin plates of nickel or similarly acting metal, the surfaceportions of which are previously oxidized. The employment of nickelshapes having the surface portion oxidized is believed to be broadlynew, and it could not be foreseen that the effectiveness of thecatalyzer would be increased, by previously partially oxidizing thesurface portions.

We disclaim the use of nickel oxid alone, as a catalyzer, since the sameis old and well known.

While we have referred particularly to nickel as the metal to beemployed, we desire to call attention to the fact that other similarlyacting metals may be employed, such as cobalt, and the like, and we callparticular attention to the fact that mixtures or alloys of nickelcontaining small quantities of cobalt, when. oxidized on the surface,act much more vigorously as catalyzers, than either pure nickel orcobalt.

In preparingthe sheets, wire and other suitable nickel shapes, forcatalytic use. we

prefer to heat them in air, oxygen or ozone until the metal surfaceceases to be shiny and bright, or in other words until tarnished oroxidized on its surface, although such oxidation may be verysuperficial.

In the revivification of the catalyzer we find that a convenient methodof procedure is first the separation of all reaction products, such ashydrogenized oil or the like, from the plates, wires or other shapes ofnickel, which may be effected by treating the same with a suitable oilsolvent, then drying, and heatin in an atmosphere of oxy gen, ozone ora1r to a temperature of 300 C. or higher, until the nickel or othermetal has been oxidized to a slight depth, after which the catalyzerwill be subjected to the action of a reducing gas, such as hydrogen, ata temperature of 300 C. for the purpose of reducing the nickel oxid,after which the catalyzer is'again subjected to the action of air or thelike, at about 800 C. for a short time, until the surface becomes coatedover more or less of its entire surface, with a thin film of oxid.

We call attention to the fact that the method of revivifying nickel andsimilar catalyzers, as herein described, is claimed in our copen'dingapplication, Serial No. 801,641.

In regard to the treatment of oils with the reactive gases, such ashydrogen, we may state that the ordinary temperature employed in the artmay be employed, and also that the reaction may be facilitated andaccelerated by theaction of the gases under considerable pressure.

We find in using these oxid-tarnished metal shapes for hydrogenation ofoils, that the hardened fats are obtained in a remarkably clean state,and not in any phase of the hydrogenation have we observed anydiscoloration of the product, as is the case with many other catalyzersheretofore suggested.

As an example of a particular use of the nickel shapes having oxidizedsurfaces, we

call attention to the fact that nickel wire gauze, ordinarily does notoperate to produce any appreciable amount of reaction between hydrogena'nd'unsaturated oils, since said metal is not in sufficiently finelydivided condition to come into contact with any appreciable amount ofoil and hydrogen, but if this nickel wire gauzeis somewhat oxidized onits surface, as above described, it operates comparatively rapidly, andproduces a comparatively rapid hydrogenation of the oil. This result wasnot to be foreseen from any of the literature previously published onthe subject.

The term nickel shapes as used in the specification, and the claims/isintended to apply to a body composed essentially of nickel, or nickelcontaining small amounts of other metals, and is not intended to coversuch a material, as pumice stone, or the like,

which is impregnated or coated with metallic nickel.

We call attention to the fact that the nickel oxid forming the surfaceof the catalyze'rs referred to in this application, is in the form of acoherent layer, closely adhering to the metal, and is not in the form offinely divided nickel oxid, which has heretofore been suggested, as acatalyzer for use in hydrogenating oils. The nickel oxid in the formwhich we employ it, is very readily separated from the products of thereaction, while in the form of a fine powder this separation is ratherdifficult- What we claim is -1. A process of effecting catalyticreactions which comprises subjecting the materials entering thereaction, to the action of a catalytic body comprising a metal of thenickel group, in a form other than'that of extremely thin'leaves, havingat least a portion of the surface thereofoxidized.

2. A catalytic process of treating a fluid, organic material whichcomprises subjecting such a material, and a substance designed to reacttherewith, to the influence of a catalytic body consisting of a metal ina form other than that of extremely thin leaves, of which at leastportions of the surface are oxidized.

3. A process of treating oils which comprises bringing said oil and amedium capable of reacting therewith, into contact with a catalyticcomprising a metal in a form other than that of extremely thin leaves,of which at least portions of the surface are coated with a catalyticmetal oxid.

4. A process 0 hydrogenating oil containing unsaturated organic bodies,said process comprising the step of treating said oil with hydrogen inthe presence of a catalytic body comprising metal in a form other thanthat of extremely thin leaves, least portions of its surface oxidized.

5. In the art of treating oils, the step of subjecting the oil to theaction of a gas capable of combining therewith, in the presence of acatalyzer comprising a nickel shape, in a form other than that ofextremely thin leaves, portions of the surface of said nickel shapebeing oxidized.

6. A process of treating oils and other unsaturated organic bodies,which comprises subjecting said oil, in the presence of a materialcapable of reacting therewith to the action of an agitating device,including a member made of a catalytic metal, portions of the surface ofwhich are coated with a. layer of a catalytic oxid. V

7 A process of effecting catalytic reac-v tions which comprisessubjecting the mate rials entering said reaction, to the actionof acatalytic body comprising a metal of the nickel group in a formother-than very thin having at.

the presence of a catalytic body comprising nickel in a form other thanvery thin leaves, having portions of its surface oxidized.

9. A process of treating an unsaturated organic body, in the fluidstate, which comprises subjecting said body to the action of a substancecapable of reacting therewith, in the presence of a catalyzer containingnickel, and a small amount of cobalt, said catalyzer being in a formother than very thin leaves, the surface of said catalyzer beingoxidized.

10. A process of effecting catalytic reactions, WhlCh comprisessubjecting fluid materials to the action of a catalytic body comprisingnickel in a form other than thin leaves, a portion of the surfacethereof being lightly oxidized.

11. A process of effecting catalytic reactions, which comprisessubjecting fluid substances to the action of a catalytic body comprisingnickel in a form other than thin leaves of which the surface has beenoxidized to a sufficient extent onlyto remove the shiny and brightsurface appearance thereof.

In testimony whereof we have afiixed our signatures in the presence oftwo witnesses.

' Witnesses:

CHARLES WEIsMAN, THoMAs F. OKnnm.

